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Procedia Engineering 42 (2012) 283 294

20th International Congress of Chemical and Process Engineering CHISA 2012


25 29 August 2012, Prague, Czech Republic

A one-dimensional two-fluid gassolid model applied to


fluidized bed reactors: The SMR and SE-SMR processes
J. Solsvik a*, Z. Chao, H. A. Jakobsen
Department of Chem. Eng., Norwegian University of Science and Technology (NTNU), Sem Slands vei 4, N-7491 Trondheim,
Norway

Abstract

A one-dimensional two-fluid EulerianEulerian model is adopted for numerical simulations of gassolid flows in
fluidized bed reactors. The simulation results obtained with the one-dimensional model are compared with the results
of a two-dimensional model for the SMR and SE-SMR processes. For the species concentrations and temperature
predictions, the one-dimensional and two-dimensional models are in good agreement. Deviations in the simulation
results are observed between the models in the phase area fractions and gas phase velocity. The one-dimensional
model should therefore be further extended to include the effect of the gas bubbles in the dense bed zone. Moreover,
it is necessary to compensate for the radial convective flow pattern by extended conductive fluxes.

2012 Published by Elsevier Ltd. Selection under responsibility of the Congress Scientific Committee
(Petr Kluson) Open access under CC BY-NC-ND license.

Keywords: SE-SMR; SMR; fluidized bed; two-fluid model; CO2-capture; numerical simulation

1. Introduction

Steam methane reforming (SMR) is currently the predominant industrial route for hydrogen
production. The development of alternative concepts for production of hydrogen via SMR has attracted a
lot of attention. A novel concept is the sorption-enhanced steam methane reforming (SE-SMR) process,
which involves the addition of a solid sorbent into the SMR reaction system for the selective removal of

* Corresponding author.
E-mail address: jannike.solsvik@chemeng.ntnu.no

1877-7058 2012 Published by Elsevier Ltd. Open access under CC BY-NC-ND license.
doi:10.1016/j.proeng.2012.07.419
284 J. Solsvik et al. / Procedia Engineering 42 (2012) 283 294

Nomenclature

Latin Letters
Cp Heat capacity
D Diffusion coefficient
d Diameter
G Modulus of elasticity
g Gravity
h Heat transfer coefficient
H Tube height
H Heat of reaction
kk Thermal conductivity of phase k
% Interfacial drag force

p Pressure
i
Q Interfacial heat transfer
Ri Reaction rate of reaction i
Rj Formation rate of component j
T Temperature
t Time
v Velocity
w Weighting function
z Axial reactor dimension
Greek Letters
Sorbent-to-catalyst ratio
Inter-phase drag coefficient
Area phase fraction
Interfacial mass flux
Shear stress
Dynamic viscosity
Density
Mass fraction
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Subscript
g Gas phase
i Reaction number
j Species type
k Phase (k=g,s)
mf minimum fluidization
p Particle
s Solid phase
t Tube
Superscript
Cap CO2 capture reaction
eff Effective
in Inlet, i.e. z = 0
m Molecular
out Outlet, i.e. z = H
s Superficial
SMR Reactions of steam methane reforming
T Turbulent

CO2; and thereby, shifting the equilibrium toward increased hydrogen production. A regeneration step
where the CO2 is released from the sorbent; and thus re-introduce the capture activity, is necessary to
make the SE-SMR process economically viable. Hence, the characteristic sorbent reactant utilized in the
SE-SMR processes must be exposed to different reactor operation conditions in a cyclic manner. The SE-
SMR process thus consists of two main steps: (i) reforming and (ii) regeneration. Because of the
heterogeneous nature of the SE-SMR reactions and the relatively short chemical activity life-time of the
sorbent, the circulating fluidized bed is a suitable reactor concept that provides possible continuous
operation of the process where the solid flux circulating between the reformer and regenerator reactor
units aims to successively recover and utilize the chemical activity of the sorbent.
Mathematical modeling and simulations of the SE-SMR process operated in fluidized bed reactors
have been performed ranging from the simpler Kunii-Levenspiel type models [1] to rigorous two-fluid
models based on kinetic theory of granular flows (KTGF) [25]. Adopting a Kunii-Levenspiel type of
model [6] the solids are commonly assumed to be stagnant in the reactor. Moreover, considering the
circulating fluidized bed design, a prescribed inter-transferred solid flux between the reactor units is
required. The SE-SMR process is dynamic in nature as the solid density and thus the flow behaviour like
the solid flux changes with time and reaction performance. Hence, the Kunii-Levenspiel models are not
appropriate to describe dynamic processes such as the SE-SMR technology. On the other hand, the two-
fluid EulerianEulerian models [7] treat the gas and solid particles as inter-penetrating continuous fluids.
Hence, a solid flux is incorporated in the two-fluid model which allows for dynamic modeling of
interconnected fluidized bed reactors. Lun et al. [8] and Gidaspow [9] have derived KTGF models which
286 J. Solsvik et al. / Procedia Engineering 42 (2012) 283 294

have been widely adopted for modeling and simulation of fluidized bed reactors, e.g. the cold-flow
studies of Lindborg et al. [10] and Wang et al. [11]
Two- and three dimensional two-fluid models are yet too computational demanding due to the
complexity of the gassolid flow in the fluidized bed reactors. Moreover, chemical reactions and the
handling of large geometries of commercial reactors challenge the presently available computing
capacity. In particular, the computations becomes excessively time consuming for the additional
consideration of interconnected reactors in a circulating fluidized bed design because the dynamic solid
fluxes exchanging between the fluidized bed reactors needs to be incorporated in the numerical solution
algorithm. Such simulations are highly relevant and important in the progress of commercial fluidized bed
reactors for processes such as the novel SE-SMR technology. A one-dimensional two-fluid model has the
advantages of considerable lower computational costs relative to the two- and three dimensional models.
Whereas details; such as the bubble wakes and multidimensional flow phenomena like circulation cells or
vortices, in the complex gas-solid flow within a fluidized bed reactor is averaged out and lost with a one-
dimensional model, the chemical reactor performance and the important solid fluxes transferred between
the reactors in a interconnected fluidized bed design, may be accurately predicted by a one-dimensional
model.
In the present study, a one-dimensional two-fluid gassolid model is adopted for numerical simulation
of the SMR and SE-SMR processes. The simulation results obtained with the one-dimensional model are
compared with the results of a two-dimensional model. The present validation study of the one-
dimensional model is performed to elucidate whether the model can be reasonably adopted for further
simulations of interconnected fluidized bed reactors with a dynamic solid flux transferred between the
reactor units. Dynamic solid circulation between fluidized bed units that operate at different conditions is
an inherent requirement for the novel SE-SMR technology operated in fluidized bed reactors. A less
computational demanding one-dimensional model to study the performance of interconnected reactor
units will be an important contribution to the progress of the commercialization of circulating fluidized
bed reactors intended for the SE-SMR technology.
The SE-SMR process can be operated using either a combined catalyst/sorbent pellet design unifying
the catalytic and capture properties in a single pellet [1214], or separate the catalytic and capture
properties into two different pellet types. For simulation studies of the SE-SMR process using the two-
pellet design, a multi-fluid Eulerian model may be derived giving the possibility for a catalyst phase,
sorbent phase and gas phase; e.g., the cold flow model of Chao et al. [15] and the SE-SMR study by
Carlo et al. [16]. Recently, Solsvik and Jakobsen [17] and Rout et al. [18] performed a numerical study of
a pellet holding both catalytic and capture properties with the objective to investigate the SE-SMR
process. With this pellet design the Eulerian model holds a single solid phase that interpenetrates with the
gas phase. Rout and Jakobsen [19] extended the pellet study adopting the novel pellet design in fixed
packed bed simulations. In the present study, the one-pellet design is adopted.

2. Chemical reactions

The conventional SMR reactor utilizes a nickel-based catalyst to produce synthesis gas from a high-
temperature mixture of methane and steam. The reforming reactions (1) and (2), and the watergas-shift
reaction (3) are the most important reactions when converting methane in the presence of steam. When a
Ca-based sorbent is integrated in the SMR process, the presumable selective removal of CO2 is
represented by reaction (4).
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CH 4 + H 2 O = CO + 3H 2 H 298 = 206.2 kJ/mol (1)


CH 4 + 2H 2 O = CO 2 + 4H 2 H 298 = 164.7 kJ/mol (2)
CO + H 2 O = CO 2 + H 2 H 298 = 41.5 kJ/mol (3)
CO 2 + CaO = CaCO3 H 298 = 178 kJ/mol (4)

In this study, the reaction kinetic model of the reforming and shift reactions by Xu and Froment [20]
and the CO2 capture for dolomite sorbents by Sun et al. [21] were adopted.

3. Two-phase model

In the present study, a one-dimensional two-fluid EulerianEulerian model describing gassolid flows
with the complexity of chemical reactions in fluidized bed reactors is derived. The governing equations
are presented by relations (5) to (10) and the constitutive equations are presented in Appendix A. Further
details on the constitutive equations and the numerical solution algorithm using the finite volume method
[2223] are given by Lindborg [24].
Continuity equation for phase k (=g,s):


(k k ) + (k k vk ) = k (5)
t z

Momentum equation for gas phase:

pg 4g g ,wall g
(g g vg ) + (g g vg vg ) = g + + g g g z + %g (6)
t z z dt z

Momentum equation for solid phase:

pg 4s s ,wall s
(s s vs ) + (s s vs vs ) = s + + s s g z G (g ) s + %s (7)
t z z dt z z

Species mass balances for phase k (=g,s):


(k k k , j ) + (k k vk k , j ) = (k k Dkeff, j k , j ) + Rk , j (8)
t z z z

Temperature equation for gas phase:

Tg Tg T
g g Cpg + g g Cpg vg = (g k geff g ) + ( H iSMR )RiSMR + Qgi (9)
t z z z i

Temperature equation for solid phase:


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Ts T T
s s Cps + s s Cps vs s = (s kseff s ) + (H Cap ) R Cap Qgi (10)
t z z z

4. Results and discussion

An in-house code for a one-dimensional two-fluid EulerianEulerian model has been developed for
fluidized bed reactors. The one-dimensional model has been applied to simulate the SMR and SE-SMR
processes and the results have been compared with the results of a two-dimensional model. A cross-
sectional averaging operator is adopted to present the results of the two-dimensional model in a
corresponding one-dimensional representation:

i Ai
< >A =
da
A i
(11)
da A
A

The reactor operation conditions and numerical parameters are presented in Table 1.
For both the SMR and SE-SMR processes, Figure 1 presents the one-dimensional and two-dimensional
model predictions of the dry mole fractions of CO, CO2, CH4 and H2 at the reactor outlet as a function of
time. Minor differences are observed in the prediction of the chemical reactor performance between the
one- and two-dimensional models. The differences in the simulation results obtained by the one- and two-
dimensional models the very first simulation seconds are related to the start-up of the multiphase reactive
flow algorithms. Nevertheless, the presence of the sorbent in the novel SE-SMR process significantly
favours the product side of the reformer and watergas-shift reactions (1)-(3), i.e., formation of H2,
relative to the commercial SMR process.
The dry mole fraction of CO2 and the temperature obtained by the one- and two-dimensional models;
as a function of the reactor length, are presented in figure 2 (SMR and SE-SMR). The prediction of the
dry mole fraction of CO2 of the SE-SMR process (Figure 2(a)) differs for the one- and two-dimensional
models close to the reactor inlet. However, except at the reactor entrance, only minor differences in the
CO2 concentration profiles are observed in the two model solutions. On the other hand, for the SMR
process (Figure 2(c)) the solutions obtained with the one- and two-dimensional models are almost
identical for the CO2 concentration. The deviation in the model predictions of the SMR and SE-SMR
processes must be related to the presence of the sorbent in the SE-SMR process; the mass transfer of CO2
between the gas and solid phases in the SE-SMR process influences on the source terms of the gas and
solid continuity equations. On the other hand; with extended conductivity fluxes according to Eq. (21),
good agreement between the two model solutions are obtained for the temperature profile within the SE-
SMR reactor (Figure 2(b)). The one-dimensional model temperature differences can be reduced by further
fitting the effective conductivity value to the two-dimensional model results. Moderately different bed
expansions are obtained with the one- and two-dimensional models giving temperature differences at the
transition zone between the dense bed and free board. Considering the SMR process (Figure 2(d)), the
one-dimensional model shows a larger temperature drop at the reactor entrance relative to the two-
dimensional model. Large convective mixing of solids is inherent in the two-dimensional model due to
the multidimensional macroscopic flow pattern.
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Fig. 1. Dry mole fractions at the reactor outlet, i.e. z=H, as a function of time for CO, CO2, CH4 and H2. Simulation results of one-
dimensional model and cross-sectional average of two-dimensional model. SMR and Se-SMR processes.
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(a)SE-SMR (b) SE-SMR

(c) SMR (d) SMR


Fig. 2. Simulation results of one-dimensional model and cross-sectional average of two-dimensional model. Temperature and dry
mole fraction of CO2. The SMR and SE-SMR processes. Simulation time: 40s.

Fig. 3. Area fraction of solid phase and gas phase velocity. The SMR process. Simulation results of one-dimensional model and
cross-sectional average of two-dimensional model. Simulation time: 40s.
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Table 1. Simulation conditions and numerical parameters.

Parameter Unit Value


dp (m) 20510-6
H (m) 0.7
out
p (Pa) 1.1105
s,mf (-) 0.6
t (s) 10-4
steam-to-carbon-ratio (-) 3
z (m) 0.01
dt (m) 0.1
3
p (kg/m ) 2000
vgs,in (m/s) 0.096
in
T (K) 873
p (-) 2.5

5. Conclusion

In the present study, an in-house code is developed of a one-dimensional two-fluid EulerianEulerian


model describing gassolid flows within fluidized bed reactors. The reactive flow simulations of the SMR
and SE-SMR processes are compared with the results of a two-dimensional model. Validation of the one-
dimensional model is performed to elucidate whether the model can be reasonably adopted for simulation
of the two interconnected fluidized bed reactors with a dynamic solid flux transferred between the reactor
units. The dynamic solid circulation between fluidized beds units operated at different conditions is an
inherent requirement for the novel SE-SMR technology. Hence, a less computational demanding model to
study the performance of interconnected reactor units will be an important contribution to the progress of
the commercialization of circulating fluidized bed reactors intended for the SE-SMR technology.
The simulation results of the one-dimensional model are in good agreement with the two-dimensional
model considering the species concentration and temperature predictions of the SMR and SE-SMR
processes. On the other hand, fair deviations between the one- and two-dimensional models are observed
for the phase area fractions and the gas phase velocity. This deviation may be related to the gas bubble
effect that is not included in the one-dimensional model. For improved one-dimensional model solution,
the model should be further extended including the effect of gas by-pass in the dense solid bed.
292 J. Solsvik et al. / Procedia Engineering 42 (2012) 283 294

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Appendix A. Constitutive equations

The constitutive equations adopted in the two-fluid model are presented in the sequent.
Stress:

vk
k = kt where t = 103 m , sm = 1 (12)
z

Wall friction stress [9]

f k k vk vk
s ,wall = (13)
2

Interfacial force [9]

%g = %s = (vs vg ) (14)

s2 gm g | U g U s | s 3 C D | U g U s | g s g
2.65

= (1 w)(150 + 1.75 ) + w( ) (15)


g d p2 dp 4 dp

atan(150(g 1))
w= + 0.5 (16)

24(1 + 0.15Re 0.687


p )
CD = , Re p < 1000
Re p (17)
CD = 0.44, Re p >= 1000

Effective gas phase diffusivity:

gt
Dgeff,j = Dgm, j + (18)
g Sct

Molecular diffusion coefficient (Wilke [25]):

1 g , j 1
Dgm, j = (19)
Mg n g ,r
M
r =1 D jr
r
r j

Binary diffusion coefficient [26]:


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0.00266101325 Tg3/ 2
D jr = (20)
0.012 p jr 2jr M 1/jr 2

Effective conductivity:

t
kkeff = kkm + k t C with C = 105 (21)
k Pr

Molecular conductivity:

k gstat
k gm = (1 s ) (22)
g

k gstat
k sm = ( A + (1 )) (23)
s

=
2
[ A 1 2 B ln A B 1 1 ( B + 1)] (24)
1 B / A (1 B / A) A B 1 B / A 2

k sstat
A= (25)
k gstat

n
k gstat = y (
j
j j +  jT +  jT 2 + jT 3 ) (26)
10/9

B = 1.25 s (27)
g

= 7.26103 (28)

Interfacial heat transfer:

6s
Qgi = hgs (Ts Tg ) (29)
dp
Interfacial heat transfer coefficient:

kg
hgs = [(7 10
g + 5g2 )(1 + 0.7Re0.2
p Pr
1/3
) + (1.33 2.4g + 1.2g2 )Re0.7
p Pr
1/3
] (30)
dp